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Relation Between the Local Structure and Solid Solubility of the Layered Material LiMO2 (M = Co, Ni, Fe) in Li2MnO3

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Abstract

Although low solid solubility and activity of LiFeO2 in xLi2MnO3·(1–x)LiFeO2 limit its practical application, it still has the potential to become a new-generation cathode material without cobalt or nickel for Li-ion batteries. In order to understand the effects of the local structures of different LiMO2 (M = Co, Ni, Fe) layered materials on their solid solubility in Li2MnO3, partial densities of states are calculated to determine the Jahn–Teller distortion in the layered cathode material, and the first-principles calculation method based on density functional theory is used to optimize and compare the local structures of LiCoO2, LiNiO2, LiFeO2, LiMnO2, and Li2MnO3. The degrees of distortion of the transition metal–oxygen (M–O) and lithium–oxygen (Li–O) octahedra in the crystal structure of the material are evaluated. It is clear that the solid solubility of layered materials is related to the bond lengths and degrees of distortion of the M–O and Li–O octahedra. Among them, the similar bond length of LiNiO2 and Li2MnO3 and the high distortion of NiO6 enhance the solid solubility of LiNiO2 in Li2MnO3. Owing to the absence of Jahn–Teller distortion in LiFeO2 and LiCoO2, the FeO6 and CoO6 octahedra are slightly distorted, thereby decreasing the solid solubility of LiMO2 (M = Fe, Co) in Li2MnO3. Understanding the relation between intra-octahedral distortion and solid solubility provides simple and efficient evidence for comparing the solid solubilities of different LiMO2 layered materials in the Li2MnO3 of Li-rich cathode materials. This study can be used as a reference for component design in Li-rich materials.

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Acknowledgements

This work was supported by Beijing Municipal Education Commission (KZ201910005003).

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Authors and Affiliations

  1. Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry, The Faculty of Environment and Life, Beijing University of Technology, Beijing, 100124, People’s Republic of China

    Chen Hou, Xiang Xiao, Yi-Ran Xing, Le-Le Yu, Yong-Heng Si, Han Lu & Yu-Juan Zhao

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  1. Chen Hou
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Hou, C., Xiao, X., Xing, YR. et al. Relation Between the Local Structure and Solid Solubility of the Layered Material LiMO2 (M = Co, Ni, Fe) in Li2MnO3. Electron. Mater. Lett. 18, 104–111 (2022). https://doi.org/10.1007/s13391-021-00316-6

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